JP7119362B2 - Mixed filament yarn, fabric, fiber-reinforced molded article and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a mixed yarn, a fabric, a fiber-reinforced molded article, and a method for producing the same.

Fiber-reinforced molded articles are used in a wide range of applications, such as transportation equipment (vehicles (automobiles, railway vehicles, etc.), aircraft, etc.), building members, electronic equipment, medical equipment, and the like. As a matrix resin for a fiber-reinforced molded product, a cured product of a thermosetting resin has conventionally been often used. However, fiber-reinforced molded products using a cured thermosetting resin as a matrix resin have poor productivity due to the long curing time of the thermosetting resin, low impact resistance, and poor storage stability of the prepreg. There is a problem that it is bad.

In order to solve these problems, prepregs and fiber-reinforced moldings using thermoplastic resins as matrix resins have been proposed. A prepreg using a thermoplastic resin as a matrix resin is obtained by laminating a thermoplastic resin film, sheet, etc., and a reinforcing fiber sheet, and melting the film, sheet, etc. to impregnate the reinforcing fiber sheet with the thermoplastic resin. Manufactured by However, since the melt viscosity of the thermoplastic resin is high, there is a problem that the reinforcing fiber sheet is difficult to be impregnated with the thermoplastic resin. Insufficient impregnation of the reinforcing fiber sheet with the thermoplastic resin results in insufficient mechanical properties such as impact resistance of the fiber-reinforced molded article.

In order to solve this problem, fabrics such as woven fabrics and knitted fabrics containing mixed yarns of reinforcing fibers and thermoplastic resin fibers are heated to melt the thermoplastic resin fibers and impregnate the thermoplastic resin between the reinforcing fibers. A method for producing a reinforced molded product has been proposed (Patent Documents 1 and 2).

JP 2014-173196 A JP 2015-101794 A

However, the fiber-reinforced molded articles obtained by the methods of Patent Documents 1 and 2 are still insufficient in mechanical properties such as impact resistance.
The present invention provides a mixed fiber yarn and a fabric capable of obtaining a fiber-reinforced molded article having excellent mechanical properties and excellent impregnation of thermoplastic resin between reinforcing fibers when producing a fiber-reinforced molded article, as well as mechanical properties. To provide a fiber-reinforced molded article excellent in

The present invention has the following aspects.
<1> A mixed yarn containing reinforcing fibers and first thermoplastic resin fibers, wherein the first thermoplastic resin fibers are selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group and an isocyanate group. A commingled yarn comprising a melt-moldable fluororesin having at least one functional group.
<2> The mixed yarn of <1>, wherein the first thermoplastic resin fibers further contain a thermoplastic resin other than the melt-moldable fluororesin.
<3> The <1> or above, wherein the mixed yarn does not contain the melt-moldable fluororesin and further contains a second thermoplastic resin fiber containing a thermoplastic resin other than the melt-moldable fluororesin. Mixed yarn of <2>.
<4> The thermoplastic resin other than the melt-moldable fluororesin is polyamide, polyester, polycarbonate, polybutylene terephthalate, polyarylate, polyethersulfone, polyarylsulfone, aromatic polyamide, aromatic polyetherimide, polyarylene. The mixed yarn of <2> or <3>, which is at least one selected from the group consisting of sulfide, polyaryletherketone, polyamideimide, thermoplastic polyimide and liquid crystal polyester.
<5> The thermoplastic resin other than the melt-moldable fluororesin is polyamide, and the polyamide is polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 9T, polyamide 610, polyamide 612, polyamide. The mixed yarn of <2> or <3>, which is at least one selected from the group consisting of 6/66 copolymer, polyamide 6/66/610 copolymer, polyamide 6T, polyamide 6I and polyamide MXD6.
<6> The mixed yarn according to any one of <1> to <5>, wherein the melt-moldable fluororesin has a melting point of 100 to 325°C.
<7> The mixed yarn of any one of <1> to <6>, wherein the reinforcing fiber is at least one selected from the group consisting of carbon fiber, glass fiber and aramid fiber.
<8> A fabric comprising the mixed yarn according to any one of <1> to <7>.
<9> A fiber-reinforced molded article obtained by molding the fabric of <8>.
<10> Forming a laminate of the fabric of <8> and a film containing one or both of the melt-moldable fluororesin and the melt-moldable thermoplastic resin other than the fluororesin, Fiber reinforced molding.
<11> When the fabric of <8> is above the melting point of the melt-moldable fluororesin and the fabric contains a thermoplastic resin other than the melt-moldable fluororesin, other than the melt-moldable fluororesin A method for producing a fiber-reinforced molded product, in which the thermoplastic resin is heated to a melting point or higher and molded.
<12> A laminate of the fabric of <8> and a film containing either or both of the melt-moldable fluororesin and the thermoplastic resin other than the melt-moldable fluororesin is melt-moldable. A method for producing a fiber-reinforced molded product, wherein the molding is performed by heating to a temperature higher than the melting point of the fluororesin and higher than the melting point of the thermoplastic resin other than the melt-moldable fluororesin.

The mixed yarn and fabric of the present invention are excellent in the impregnating property between the reinforcing fibers of the thermoplastic resin when producing the fiber-reinforced molded product. Further, according to the mixed yarn and fabric of the present invention, it is possible to obtain a fiber-reinforced molded article having excellent mechanical properties.
The fiber-reinforced molded article of the present invention has excellent mechanical properties.
According to the method for producing a fiber-reinforced molded article of the present invention, a fiber-reinforced molded article having excellent mechanical properties can be produced.

The following term definitions apply throughout the specification and claims.
A "mixed yarn" is a yarn made by mixing two or more types of fibers.
A "multifilament" is a single thread made by bundling a plurality of single fibers.
By "continuous fiber" is meant a fiber greater than 100 mm in length.
By "melt moldable" is meant exhibiting melt flowability.
“Exhibiting melt fluidity” means that there exists a temperature at which the melt flow rate is 0.1 to 1000 g/10 minutes at a temperature 20° C. or more higher than the melting point of the resin under a load of 49 N. .
"Melting point" is the temperature corresponding to the maximum of the melting peak as measured by differential scanning calorimetry (DSC).
"Melt flow rate" is melt mass flow rate (MFR) defined in JIS K 7210-1:2014 (corresponding international standard ISO 1133-1:2011).
"Carbonyl group-containing group" means a group having a carbonyl group (-C(=O)-) in its structure.
"Acid anhydride group" means a group represented by -C(=O)-OC(=O)-.
"A unit based on a monomer" is a general term for an atomic group directly formed by polymerization of one molecule of a monomer and an atomic group obtained by chemically converting a part of the atomic group. In this specification, units based on monomers are also simply referred to as monomer units.
By "monomer" is meant a compound having a polymerizable carbon-carbon double bond.
"~" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.

<Mixed yarn>
The mixed yarn of the present invention contains reinforcing fibers and specific first thermoplastic resin fibers described later.
The mixed yarn of the present invention may optionally contain second thermoplastic resin fibers other than the first thermoplastic resin fibers as long as the effects of the present invention are not impaired. Hereinafter, the first thermoplastic resin fiber and the second thermoplastic resin fiber are collectively referred to as "thermoplastic resin fiber".
The mixed yarn of the present invention may be twisted or untwisted.

The fineness of the mixed yarn is preferably 1,000 to 100,000 dtex, more preferably 1,500 to 50,000 dtex, even more preferably 2,000 to 50,000 dtex, and particularly preferably 3,000 to 5,000 dtex. Here, the fineness of the mixed yarn is the total value of the fineness of the reinforcing fibers and the fineness of the thermoplastic resin fibers used to manufacture one mixed yarn.

The ratio of the fineness of the thermoplastic resin fiber to the fineness of the reinforcing fiber (fineness of the thermoplastic resin fiber/fineness of the reinforcing fiber) is preferably 0.1 to 10, more preferably 0.1 to 6.0, and 0.8. ~2.0 is more preferred. Here, the fineness of the thermoplastic resin fiber/the fineness of the reinforcing fiber is the ratio of the fineness of the thermoplastic resin fiber to the fineness of the reinforcing fiber used for manufacturing one mixed yarn.

The ratio of the fineness of the first thermoplastic resin fiber to the fineness of the reinforcing fiber (fineness of the first thermoplastic resin fiber/fineness of the reinforcing fiber) is preferably 0.01 to 10, and 0.01 to 6.0. More preferably, 0.04 to 2.0 is even more preferable. Here, the fineness of the first thermoplastic resin fiber/the fineness of the reinforcing fiber is the ratio of the fineness of the first thermoplastic resin fiber to the fineness of the reinforcing fiber used for manufacturing one mixed yarn.

The number of fibers in the mixed yarn is preferably 100 to 100,000 f, more preferably 1,000 to 100,000 f, more preferably 1,500 to 70,000 f, still more preferably 2,000 to 20,000 f, even more preferably 2,500 to 10,000 f, and particularly preferably 3,000 to 5,000 f. If the number of fibers in the mixed yarn is within the above range, the mixing property of the mixed yarn is improved, and a fiber-reinforced molded article having even better mechanical properties can be obtained. Here, the number of fibers in the mixed yarn is the sum of the number of reinforcing fibers and the number of thermoplastic resin fibers used to produce one mixed yarn.

The ratio of the number of thermoplastic resin fibers to the number of reinforcing fibers (number of thermoplastic resin fibers/number of reinforcing fibers) is preferably 0.001 to 1, more preferably 0.001 to 0.5. , 0.05 to 0.2 are more preferred. If the number of fibers of the thermoplastic resin fiber/the number of fibers of the reinforcing fiber is within the above range, the mixing property of the mixed yarn is improved, and a fiber-reinforced molded article having even better mechanical properties can be obtained. Here, the number of thermoplastic resin fibers/the number of reinforcing fibers is the ratio of the number of thermoplastic resin fibers to the number of reinforcing fibers used to produce one mixed yarn.

(reinforced fiber)
Examples of reinforcing fibers include inorganic fibers, metal fibers, and organic fibers.
Examples of inorganic fibers include carbon fibers, graphite fibers, glass fibers, silicon carbide fibers, silicon nitride fibers, alumina fibers, silicon carbide fibers, and boron fibers.
Examples of metal fibers include aluminum fibers, brass fibers, stainless steel fibers, and the like.
Organic fibers include aromatic polyamide fibers, polyaramid fibers, polyparaphenylenebenzoxazole (PBO) fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, and polyethylene fibers.

Reinforcing fibers may be used singly or in combination of two or more.
The reinforcing fibers may be continuous fibers or discontinuous fibers. As the reinforcing fibers, continuous fibers are preferable from the viewpoint of easy production of mixed yarns.
The reinforcing fibers may be surface-treated.

As the reinforcing fiber, at least one selected from the group consisting of carbon fiber, glass fiber and aramid fiber is preferable from the viewpoint of excellent strength and lightness, and carbon fiber is preferable from the viewpoint of low specific gravity, high strength and high elastic modulus. Fibers are more preferred.
Examples of carbon fibers include those described in WO2013/129169, preferably those described in paragraphs [0018] to [0026]. Carbon fibers can be produced by a known production method.

The fineness of the reinforcing fiber is preferably 100 to 50,000 dtex, more preferably 500 to 40,000 dtex, still more preferably 1,000 to 10,000 dtex, and particularly preferably 1,000 to 3,000 dtex per mixed yarn. If the fineness of the reinforcing fiber per mixed yarn is within the above range, the production of the mixed yarn is facilitated, and a fiber-reinforced molded article having even better mechanical properties can be obtained.

The number of reinforcing fibers per mixed yarn is preferably 500 to 50,000 f, more preferably 500 to 20,000 f, still more preferably 1,000 to 10,000 f, and particularly preferably 1,500 to 5,000 f. If the number of reinforcing fibers per mixed yarn is within the above range, the reinforcing fibers are well dispersed in the mixed yarn.

(First thermoplastic resin fiber)
The first thermoplastic resin fibers contain a specific fluororesin A, which will be described later.
The first thermoplastic resin fiber further contains a thermoplastic resin other than the fluororesin A (hereinafter also referred to as "another thermoplastic resin") as necessary within a range that does not impair the effects of the present invention. good too.
The first thermoplastic resin fiber further contains a fluororesin A and other components other than the thermoplastic resin (hereinafter also referred to as "other components") as necessary within a range that does not impair the effects of the present invention. You can
The proportion of fluororesin A in the first thermoplastic resin fibers is preferably 1 to 100% by mass, more preferably 5 to 100% by mass. The proportion of fluororesin A may be 100% by mass.

The first thermoplastic resin fibers may be used singly or in combination of two or more having different components.
The first thermoplastic resin fibers may be continuous fibers or discontinuous fibers. As the first thermoplastic resin fibers, continuous fibers are preferable from the viewpoint of easy production of mixed yarns.
The first thermoplastic resin fibers may be surface-treated.
The first thermoplastic resin fibers may be twisted or untwisted.

The first thermoplastic resin fiber is produced by spinning a fluororesin A or a resin composition containing the fluororesin A by a known spinning method. A spinning method includes a melt spinning method. The first thermoplastic resin fibers obtained by spinning are processed into multifilaments, monofilaments, etc. by known methods.
The composition containing fluororesin A is prepared by mixing each component in advance using various mixers such as a tumbler and a Henschel mixer, followed by a Banbury mixer, rolls, Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader. It is prepared by melting and kneading with

The first thermoplastic resin fibers are usually used in the production of a mixed yarn as a first thermoplastic resin fiber bundle in which a plurality of fibers are bundled.
The fineness of the first thermoplastic resin fiber bundle is preferably 40 to 600 dtex, more preferably 50 to 500 dtex, even more preferably 100 to 400 dtex. If the fineness of the first thermoplastic resin fiber bundle is within the above range, the first thermoplastic resin fibers are well dispersed in the mixed yarn.

The number of fibers in the first thermoplastic resin fiber bundle is preferably 1 to 200 f, more preferably 5 to 100 f, still more preferably 10 to 80 f, and particularly preferably 20 to 50 f. When the number of fibers in the first thermoplastic resin fiber bundle is within the above range, the first thermoplastic resin fibers are well dispersed in the mixed yarn.

(Fluororesin A)
The fluororesin A has at least one functional group (hereinafter referred to as "adhesive functional group") selected from the group consisting of carbonyl group-containing groups, hydroxy groups, epoxy groups and isocyanate groups. The fluororesin A may be used alone or in combination of two or more.

The adhesive functional group is either one or both of the terminal group of the main chain of the fluororesin A and the pendant group of the main chain, since the moldability of the fluororesin A when melted and the impregnation between reinforcing fibers are further excellent. It is preferred to exist as The number of adhesive functional groups may be one, or two or more.

The fluororesin A preferably has at least a carbonyl group-containing group as an adhesive functional group from the viewpoint of better impregnation between reinforcing fibers.
The carbonyl group-containing group includes a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride group, and the like.

Examples of the hydrocarbon group in the group having a carbonyl group between carbon atoms of the hydrocarbon group include an alkylene group having 2 to 8 carbon atoms. The number of carbon atoms in the alkylene group is the number of carbon atoms not including the carbon atoms that constitute the carbonyl group. The alkylene group may be linear or branched.
A haloformyl group is represented by -C(=O)-X (where X is a halogen atom). The halogen atom in the haloformyl group includes a fluorine atom, a chlorine atom and the like, and a fluorine atom is preferred.
The alkoxy group in the alkoxycarbonyl group may be linear or branched, preferably an alkoxy group having 1 to 8 carbon atoms, more preferably a methoxy group or an ethoxy group.

The content of the adhesive functional group in the fluororesin A is preferably 10 to 60,000, more preferably 100 to 50,000, even more preferably 100 to 10,000 per 1×10 ⁶ carbon atoms in the main chain of the fluororesin A. 300 to 5000 are particularly preferred. When the content of the adhesive functional group is at least the lower limit of the above range, the impregnation between the reinforcing fibers is remarkably excellent. If the content of the adhesive functional group is equal to or less than the upper limit of the above range, processing into fibers becomes possible without high temperature conditions during spinning.

The content of adhesive functional groups can be measured by methods such as nuclear magnetic resonance (NMR) analysis and infrared absorption spectroscopy. For example, using a method such as infrared absorption spectrum analysis as described in JP-A-2007-314720, the ratio (mol%) of units having an adhesive functional group in all units constituting the fluororesin A is determined. The content of the adhesive functional group can be calculated from this ratio.

The melting point of the fluororesin A is preferably 100 to 325°C, more preferably 120 to 315°C, even more preferably 150 to 310°C. If the melting point of the fluororesin A is at least the lower limit of the above range, the heat resistance of the mixed yarn, fabric and fiber-reinforced molded product will be excellent. If the melting point of the fluororesin A is equal to or lower than the upper limit of the above range, a general-purpose apparatus can be used during spinning and production of fiber-reinforced moldings.
The melting point of the fluororesin A can be adjusted by the type of units constituting the fluororesin A, the ratio of the units, the molecular weight of the fluororesin A, and the like. For example, the melting point tends to increase as the proportion of the unit u1, which will be described later, increases.

As the fluororesin A, a material that can be melt-molded is used because it facilitates the production of the first thermoplastic resin fiber and the fiber-reinforced molding.
As the melt-moldable fluororesin A, known melt-moldable fluororesins (tetrafluoroethylene-fluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer fluororesin obtained by introducing an adhesive functional group into (coalescence, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, etc.).

As the fluororesin A, one having a melt flow rate of 0.1 to 1000 g/10 minutes at a temperature higher than the melting point of the fluororesin A by 20° C. or more under a load of 49 N is used. The melt flow rate is preferably 0.5-100 g/10 min, more preferably 1-30 g/10 min, and even more preferably 5-20 g/10 min. When the melt flow rate is at least the lower limit of the above range, the fluororesin A is excellent in processability into fibers. If the melt flow rate is equal to or lower than the upper limit of the above range, the mechanical properties of the mixed yarn, fabric and fiber-reinforced molded product will be further improved.

Examples of the fluororesin A include the following depending on the difference in production method.
- A fluoropolymer having an adhesive functional group derived from at least one selected from the group consisting of a monomer, a chain transfer agent and a polymerization initiator used in the production of the fluoropolymer (hereinafter referred to as "containing Also referred to as "fluoropolymer A1").
• A fluororesin obtained by introducing an adhesive functional group into a fluororesin having no adhesive functional group by surface treatment such as corona discharge treatment or plasma treatment.
• A fluororesin obtained by graft polymerization of a monomer having an adhesive functional group to a fluororesin having no adhesive functional group.

As the fluororesin A, the fluoropolymer A1 is preferable for the following reasons.
-In the fluoropolymer A1, the adhesive functional group is present in one or both of the terminal group of the main chain and the pendant group of the main chain of the fluoropolymer A1, so that the processability to fibers is remarkably excellent. .
・The adhesive functional groups introduced into the fluororesin by surface treatment are unstable and tend to disappear over time.

When the adhesive functional group in the fluoropolymer A1 is derived from the monomer used for producing the fluoropolymer A1, the fluoropolymer A1 can be produced by Method 1 below. In this case, the adhesive functional groups are present in the monomer units.
Method 1: A monomer having an adhesive functional group is used in producing the fluoropolymer A1 by polymerization of the monomer.

When the adhesive functional group in the fluoropolymer A1 is derived from the chain transfer agent used in the production of the fluoropolymer A1, the fluoropolymer A1 can be produced by Method 2 below. In this case, the adhesive functional group exists as a terminal group of the main chain of the fluoropolymer A1.
Method 2: A fluoropolymer A1 is produced by polymerization of monomers in the presence of a chain transfer agent having an adhesive functional group.
Chain transfer agents having an adhesive functional group include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

When the adhesive functional group in the fluoropolymer A1 is derived from the polymerization initiator used for producing the fluoropolymer A1, the fluoropolymer A1 can be produced by Method 3 below. In this case, the adhesive functional group exists as a terminal group of the main chain of the fluoropolymer A1.
Method 3: A fluoropolymer A1 is produced by polymerizing a monomer in the presence of a polymerization initiator such as a radical polymerization initiator having an adhesive functional group.
Radical polymerization initiators having adhesive functional groups include di-n-propylperoxydicarbonate, diisopropylperoxycarbonate, tert-butylperoxyisopropylcarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, di-2- and ethylhexyl peroxydicarbonate.

When the adhesive functional groups in the fluoropolymer A1 are derived from two or more of the monomer, chain transfer agent, and polymerization initiator used in the production of the fluoropolymer A1, the fluoropolymer A1 can be produced by using two or more of the above methods 1 to 3 in combination.
As the fluoropolymer A1, the content of the adhesive functional group can be easily controlled, and therefore the impact resistance of the fiber-reinforced molded product can be easily adjusted. It is preferable to have an adhesive functional group that

Examples of the monomer having an adhesive functional group include monomers having a carboxy group (maleic acid, itaconic acid, citraconic acid, undecylenic acid, etc.), monomers having an acid anhydride group (itaconic anhydride (hereinafter referred to as Also referred to as "IAH".), citraconic anhydride (hereinafter also referred to as "CAH"), 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), maleic anhydride, etc.) , a monomer having a hydroxyl group and an epoxy group (hydroxybutyl vinyl ether, glycidyl vinyl ether, etc.), and the like.

As the fluoropolymer A1 having an adhesive functional group derived from a monomer, the following fluoropolymer A1 is particularly preferred from the viewpoint that the moldability of the fluoropolymer A1 when melted is remarkably excellent.
A unit u1 based on tetrafluoroethylene (hereinafter also referred to as “TFE”) or chlorotrifluoroethylene (hereinafter also referred to as “CTFE”), a unit u2 based on an acid anhydride group-containing cyclic monomer, and a fluorine-containing polymer A1 having units u3 based on fluorine monomers (excluding TFE and CTFE);
Here, the acid anhydride group possessed by the unit u2 corresponds to the adhesive functional group.

Acid anhydride group-containing cyclic monomers constituting unit u2 include IAH, CAH, NAH, maleic anhydride, and the like. The acid anhydride group-containing cyclic monomer may be used alone or in combination of two or more.
As the acid anhydride group-containing cyclic monomer, one or more selected from the group consisting of IAH, CAH and NAH are preferable. When one or more selected from the group consisting of IAH, CAH and NAH is used, acid anhydride can be produced without using a special polymerization method (see JP-A-11-193312) that is required when maleic anhydride is used. Fluorine-containing polymer A1 having a physical group can be easily produced.
As the acid anhydride group-containing cyclic monomer, IAH or NAH is preferable from the viewpoint of remarkably excellent processability into fibers.

The fluorine-containing monomer constituting the unit u3 is preferably a fluorine-containing compound having one polymerizable carbon-carbon double bond, and fluoroolefins (vinyl fluoride, vinylidene fluoride, trifluoroethylene, hexafluoropropylene ( hereinafter also referred to as “HFP”), hexafluoroisobutylene, etc., excluding TFE), CF ₂ =CFOR ^f1 (where R ^f1 has 1 to 10 carbon atoms and may contain an oxygen atom between carbon atoms) (hereinafter also referred to as “PAVE”), CF ₂ ═CFOR ^f2 SO ₂ X ¹ (wherein R ^f2 is a perfluoroalkyl group having 1 to 10 carbon atoms which may contain an oxygen atom between carbon atoms); an alkylene group, and X ¹ is a halogen atom or a hydroxyl group), CF ₂ ═CFOR ^f3 CO ₂ X ² (wherein R ^f3 is a perfluoroalkylene having 1 to 10 carbon atoms and which may contain an oxygen atom between carbon atoms and X ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.), CF ₂ =CF(CF ₂ ) _p OCF=CF ₂ (where p is 1 or 2), CH ₂ =CX ³ (CF ₂ ) _q X ⁴ (where X ³ is a hydrogen atom or a fluorine atom, q is an integer of 2 to 10, and X ⁴ is a hydrogen atom or a fluorine atom) (hereinafter referred to as Also referred to as “FAE”.), fluorine-containing monomers having a ring structure (perfluoro(2,2-dimethyl-1,3-dioxole), 2,2,4-trifluoro-5-trifluoromethoxy-1, 3-dioxole, perfluoro (2-methylene-4-methyl-1,3-dioxolane), etc.).

The fluoromonomer is preferably at least one selected from the group consisting of HFP, PAVE and FAE, more preferably one or both of FAE and HFP, from the viewpoint of excellent moldability of the fluoropolymer A1. .
As PAVE, CF2 _{= CFOCF2CF3} , CF2 _{= CFOCF2CF2CF3 (} hereinafter also referred to as "PPVE"), _{CF2 = CFOCF2CF2CF2CF3 , CF2 = CFO (} CF ₂ ) ₆ F, etc., and PPVE is preferred.

As FAE, _CH2 =CF(CF2) _2F , _CH2 =CF(CF2) _3F , _CH2 =CF _{( CF2} )4F, _{CH2 =} CF _{( CF2} ) _5F , _CH2 =CF(CF2) _6F , _CH2 =CF(CF2) _2H , _CH2 =CF( _CF2 ) _3H , _{CH2 =} CF( _CF2 ) _4H , _{CH2 =} CF ₍ CF2) 5H, _{CH2 =} CF ₍ CF2)6H, _CH2 =CH(CF2) _2F (hereinafter referred to as " _PFEE "), _{CH2 =} CH(CF2) _3F , _{CH2 =} CH (CF2)4F (hereinafter referred to as " _PFBE "), _{CH2 =} CH _{( CF2} )5F, _{CH2 =} CH ₍ CF2)6F, _{CH2 =} CH ₍ CF2)2H, _CH2 =CH(CF2) _3H , _{CH2 =} CH( _CF2 ) _4H , _CH2 =CH( _CF2 ) _5H , _CH2 =CH( _CF2 ) _6H and the like.
FAE is preferably CH ₂ ═CH(CF ₂ ) _q1 X ⁴ (where q1 is 2 to 6, preferably 2 to 4), PFEE, CH ₂ ═CH(CF ₂ ) ₃ F, _PFBE , _CH2 =CF ₍ CF2) _3H and _{CH2 =} CF(CF2)4H are more preferable, and PFEE or PFBE is particularly preferable.

The fluoropolymer A1 may have a unit u4 based on a non-fluorine monomer (excluding an acid anhydride group-containing cyclic monomer) in addition to the units u1 to u3.
The non-fluorine monomer is preferably a compound having one polymerizable carbon-carbon double bond, and examples thereof include olefins (ethylene, propylene, 1-butene, etc.) and vinyl esters (vinyl acetate, etc.). A non-fluorine monomer may be used individually by 1 type, and may use 2 or more types together.
As the non-fluorine monomer, ethylene, propylene and 1-butene are preferable, and ethylene is particularly preferable, from the viewpoint of further excellent processability into fibers.

When the unit u4 is an ethylene unit (hereinafter also referred to as "E unit"), preferred ratios of each unit are as follows.
The ratio of unit u1 is preferably 25 to 79.79 mol%, more preferably 40 to 64.47 mol%, more preferably 45 to 61.95 mol, of the total of unit u1, unit u2, unit u3 and unit u4. % is more preferred.
The ratio of unit u2 is preferably 0.01 to 5 mol%, more preferably 0.03 to 3 mol%, and 0.05 to 1 mol of the total of unit u1, unit u2, unit u3, and unit u4. % is more preferred.
The ratio of unit u3 is preferably 0.2 to 20 mol%, more preferably 0.5 to 15 mol%, and 1 to 12 mol% of the total of unit u1, unit u2, unit u3 and unit u4. More preferred.
The ratio of unit u4 is preferably 20 to 74.79 mol%, more preferably 35 to 50 mol%, and 37 to 53.95 mol% of the total of unit u1, unit u2, unit u3 and unit u4. More preferred.

Preferred proportions of each unit when not having unit u4 are as follows.
The proportion of unit u1 is preferably 50 to 99.89 mol%, more preferably 50 to 99.4 mol%, and further 50 to 98.9 mol% of the total of unit u1, unit u2 and unit u3. preferable.
The ratio of unit u2 is preferably 0.01 to 5 mol%, more preferably 0.1 to 3 mol%, and further 0.1 to 2 mol% of the total of unit u1, unit u2 and unit u3. preferable.
The ratio of unit u3 is preferably 0.1 to 49.99 mol%, more preferably 0.5 to 49.9 mol%, and 1 to 49.9, of the total of unit u1, unit u2 and unit u3. Mole % is even more preferred.

If the ratio of each unit is within the above range, the flame retardancy, chemical resistance, etc. of the mixed yarn, fabric, and fiber-reinforced molded product are remarkably excellent.
When the ratio of the units u2 is within the above range, the amount of acid anhydride groups in the fluoropolymer A1 is appropriate, and the workability into fibers is remarkably excellent.
When the ratio of the units u3 is within the above range, the processability of the fluoropolymer A1 into fibers is remarkably excellent.
The ratio of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluoropolymer A1.

In the fluoropolymer A1, a part of the acid anhydride group in the unit u2 is hydrolyzed, and as a result, a dicarboxylic acid corresponding to the acid anhydride group-containing cyclic monomer (itaconic acid, citraconic acid, 5-norbornene -2,3-dicarboxylic acids, maleic acid, etc.). When a dicarboxylic acid-based unit is included, the proportion of the dicarboxylic acid-based unit shall be included in the proportion of the unit u2.

Preferred specific examples of the fluoropolymer A1 include the following.
a copolymer having TFE units, NAH units and PPVE units;
a copolymer having TFE units, IAH units and PPVE units;
a copolymer having TFE units, CAH units and PPVE units;
a copolymer having TFE units, IAH units and HFP units;
a copolymer having TFE units, CAH units and HFP units;
a copolymer having TFE units, IAH units, PFBE units and E units;
a copolymer having TFE units, CAH units, PFBE units and E units;
a copolymer having TFE units, IAH units, PFEE units and E units;
a copolymer having TFE units, CAH units, PFEE units and E units;
copolymers having TFE units, IAH units, HFP units, PFBE units and E units;

The fluororesin A can be produced by a conventional method. When the fluororesin A is produced by polymerization of monomers, a polymerization method using a radical polymerization initiator is preferred as the polymerization method.
As the polymerization method, a bulk polymerization method, a solution polymerization method using an organic solvent (fluorocarbon, chlorinated hydrocarbon, fluorochlorinated hydrocarbon, alcohol, hydrocarbon, etc.), an aqueous medium and, if necessary, a suitable organic solvent and an emulsion polymerization method using an aqueous medium and an emulsifier, and a solution polymerization method is preferred.

(other thermoplastic resins)
Other thermoplastic resins include polyesters (polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, liquid crystal polyester, etc.), polyolefins (polyethylene, polypropylene, polybutylene, acid-modified polyethylene, acid-modified polypropylene, acid-modified polybutylene etc.), polyoxymethylene, polyamide, polyarylene sulfide resin (polyphenylene sulfide, etc.), polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyethernitrile, fluororesin other than fluororesin A (polytetrafluoro ethylene, etc.), liquid crystal polymer, styrene resin (polystyrene, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, etc.), polycarbonate, polymethyl methacrylate, polyvinyl chloride, unmodified or modified polyphenylene ether, thermoplastic polyimide, polyamideimide, poly Etherimide, polysulfone, polyethersulfone, polyarylate, polystyrene-based elastomer, polyolefin-based elastomer, polyurethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, polybutadiene-based elastomer, polyisoprene-based elastomer, fluorine-based elastomer (However, fluorine resin A ), acrylonitrile-based elastomers, and the like.

Other thermoplastic resins include polyamides, polyesters, polycarbonates, polybutylene terephthalate, polyarylates, polyethersulfones, polyarylsulfones, aromatic polyamides, aromatic polyetherimides, polyarylene sulfides, At least one selected from the group consisting of polyaryletherketone, polyamideimide, thermoplastic polyimide and liquid crystal polyester is preferred.

As another thermoplastic resin, polyamide is preferable from the viewpoint of improving moldability and mechanical properties. Polyamides can be produced, for example, by ring-opening polymerization or polycondensation of ω-amino acids, lactams or dicarboxylic acids and diamines or the like.
ω-amino acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 2-chloro-para-aminomethylbenzoic acid, and 2-methyl-para-aminomethylbenzoic acid. acid, 4-aminomethylbenzoic acid and the like.
Lactams include ε-caprolactam, enantholactam, capryllactam, undecanelactam, lauryllactam, α-pyrrolidone, α-piperidone and the like.
Carboxylic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecadioic acid, hexadecadioic acid, hexadecenedioic acid, eicosandioic acid, eicosadienoic acid, Diglycolic acid, 2,2,4-trimethyladipic acid, xylylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid , 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like.
Examples of diamines include hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, bis-( 4,4'-aminocyclohexyl)methane, metaxylylenediamine, terephthaldiamine and the like.

Polyamides include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 9T, polyamide 610, polyamide 612, polyamide 6/66 copolymer, and polyamide, since they have an excellent balance between mechanical properties and moldability. At least one selected from the group consisting of 6/66/610 copolymer, polyamide 6T, polyamide 6I and polyamide MXD6 is more preferred, and polyamide 6, polyamide 66, polyamide 12, polyamide 9T and polyamide 6T are particularly preferred.

(other ingredients)
Other components include inorganic fillers, organic fillers, organic pigments, metallic soaps, surfactants, UV absorbers, lubricants, silane coupling agents, organic compounds (organic monomers, organic oligomers with a degree of polymerization of 50 or less, etc.). is mentioned.

Inorganic fillers include silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, water. Aluminum oxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass Beads, silica balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon burns, wood flour, zinc borate and the like. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
The inorganic filler may be surface-treated with a surface-treating agent such as a silane coupling agent or a titanate coupling agent in order to improve dispersibility in the resin.

Examples of organic fillers include aromatic polyamide fibers, polyaramid fibers, polyparaphenylenebenzoxazole (PBO) fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, and polyethylene fibers.

(Second thermoplastic resin fiber)
The second thermoplastic resin fibers do not contain fluororesin A and contain other thermoplastic resins.
Other thermoplastic resins include those similar to the other thermoplastic resins in the first thermoplastic resin fibers, and preferred forms are also the same.
The ratio of the other thermoplastic resin in the second thermoplastic resin fibers is preferably 1-100% by mass, more preferably 5-100% by mass. The proportion of other thermoplastic resins may be 100% by mass.
The second thermoplastic resin fiber may further contain other components other than the thermoplastic resin as necessary, as long as the effects of the present invention are not impaired.
Other components other than the thermoplastic resin include the same components as the other components in the first thermoplastic resin fiber, and preferred forms are also the same.

The second thermoplastic resin fibers may be used singly or in combination of two or more different components.
The second thermoplastic resin fibers may be continuous fibers or discontinuous fibers. As the second thermoplastic resin fibers, continuous fibers are preferable from the viewpoint of easy production of mixed yarns.
The second thermoplastic resin fibers may be surface-treated.
The second thermoplastic resin fibers may be twisted or untwisted.

The second thermoplastic resin fibers are manufactured in the same manner as the first thermoplastic resin fibers.
The second thermoplastic resin fibers are usually used in the production of mixed yarn as a second thermoplastic resin fiber bundle in which a plurality of fibers are bundled.
The preferred fineness and fiber count of the second thermoplastic resin fiber bundle are the same as the preferred fineness and fiber count of the first thermoplastic resin fiber bundle.

(Manufacturing method of mixed yarn)
The mixed yarn can be produced by mixing the reinforcing fibers, the first thermoplastic resin fibers and, if necessary, the second thermoplastic resin fibers by a known mixing method.
Examples of the mixed fiber method include an open fiber fused method, a fluid entanglement (interlace) method, and the like.
The open fiber merging method is a method in which each fiber is opened by an external force such as pressure from an electrostatic force, a fluid spray, or a pressure applied to a roller or the like, and then the fibers are fused and aligned while being spread.
As a fluid entangling method, a plurality of vortex turbulent zones are formed by fluids such as air, nitrogen gas, and water vapor in parallel with the yarn axis, and each fiber is guided to the vortex turbulent zones to the extent that loops and crimps do not occur. Examples include a method of forming non-bulky yarn under tension, and a method of fluidly entangling after opening only reinforcing fibers or after opening reinforcing fibers and thermoplastic resin fibers.

Specific examples of the mixed fiber method include, for example, JP-A-2-308824, JP-A-3-33237, JP-A-2-28219, JP-A-4-73227, and JP-A-9-324331. , Patent Document 1, Patent Document 2, and the like.

Reinforcing fiber bundles and thermoplastic resin fiber bundles are usually used for manufacturing the mixed yarn.
In order to satisfy the predetermined fineness and number of reinforcing fibers in one mixed yarn, one reinforcing fiber bundle may be used for manufacturing, or a plurality of reinforcing fiber bundles may be used for manufacturing. It is preferable to use 1 to 10 reinforcing fiber bundles, more preferably 1 to 3 reinforcing fiber bundles, and 1 reinforcing fiber bundle to produce one mixed yarn. is more preferred.
In order for the thermoplastic resin fibers to satisfy the predetermined fineness and number of fibers in one mixed yarn, it may be manufactured with one thermoplastic resin fiber bundle, or manufactured using a plurality of thermoplastic resin fiber bundles. You may In order to produce one mixed yarn, it is preferable to use 1 to 100 thermoplastic resin fiber bundles, more preferably 1 to 50 thermoplastic resin fiber bundles, and 3 to 15 thermoplastic resin fiber bundles. More preferably, thermoplastic resin fiber bundles are used.

(Mechanism of action)
Since the mixed yarn of the present invention described above is a mixed yarn containing reinforcing fibers and first thermoplastic resin fibers, a fiber-reinforced molded product is manufactured using a fabric obtained by processing the mixed yarn. It is excellent in the impregnation between reinforcing fibers of the thermoplastic resin. In addition, since the first thermoplastic resin fiber contains a melt-moldable fluororesin having an adhesive functional group, the adhesion between the thermoplastic resin, which is the matrix resin, and the reinforcing fiber when a fiber-reinforced molded product is formed. Excellent. Therefore, a fiber-reinforced molded article having excellent mechanical properties can be obtained.

<Fabric>
The fabric of the present invention contains the mixed yarn of the present invention. The mixed yarn of the present invention may be used singly or in combination of two or more.
The fabric of the invention may optionally contain yarns other than the mixed yarn of the invention (hereinafter referred to as "other yarns") as long as the effects of the invention are not impaired. Other yarns include mixed yarns other than the mixed yarn of the present invention, reinforcing fiber bundles, thermoplastic fiber bundles, and the like.
The fabric of the present invention may be a laminate in which two or more layers are laminated.

The form of the fabric includes woven fabric, knitted fabric, braided fabric, non-woven fabric, tow sheet and the like.
Examples of the form of the woven fabric include plain weave, eight-piece satin weave, four-piece satin weave, and twill weave. Alternatively, it may be a non-crimped fabric (non-crimped fabric) that does not have bent fibers.
Forms of knitting include warp knitting, weft knitting, and raschel knitting. It may also be a braided rope (rope).
A braid etc. are mentioned as a braid.
Non-woven fabrics include non-woven fabrics obtained by randomly laminating mixed yarns and, if necessary, other yarns in the form of continuous fibers, and integrating them by thermal fusion or entangling, mixed yarns, and other yarns, if necessary. A non-woven fabric (chopped strand mat) obtained by cutting the material into short pieces, laminating them, and integrating them by heat-sealing.
The tow sheet includes a tape-like or sheet-like base material in which mixed yarns and, if necessary, other yarns are aligned in one direction.
The fabric of the present invention is manufactured by known methods.

Since the fabric of the present invention described above includes the mixed yarn containing the reinforcing fiber and the first thermoplastic resin fiber, when manufacturing a fiber-reinforced molded product using the fabric, the thermoplastic resin Excellent impregnation between reinforcing fibers. In addition, since the first thermoplastic resin fiber contains a melt-moldable fluororesin having an adhesive functional group, the adhesion between the thermoplastic resin, which is the matrix resin, and the reinforcing fiber when a fiber-reinforced molded product is formed. Excellent. Therefore, a fiber-reinforced molded article having excellent mechanical properties can be obtained.

<Fiber reinforced molding>
The fiber-reinforced molded article of the present invention is obtained by molding the fabric of the present invention.
The fiber-reinforced molded article of the present invention may be obtained by molding a laminate of the fabric of the present invention and a film containing one or both of fluororesin A and other thermoplastic resins.

As a method for producing the fiber-reinforced molded article of the present invention, the fabric of the present invention is molded by heating the fabric of the present invention to the melting point of the fluororesin A or higher and, if other thermoplastic resin is included, to the melting point of the other thermoplastic resin or higher. method.
Further, as a method for producing the fiber-reinforced molded article of the present invention, a laminate of the fabric of the present invention and a film containing either one or both of the fluororesin A and other thermoplastic resins is prepared at the melting point of the fluororesin A In addition to the above, other thermoplastic resins may be molded by heating to a temperature higher than the melting point.

As a specific method for producing a fiber-reinforced molded product, for example, the fabric of the present invention and, if necessary, a film are placed in a mold, and the melting point of the fluororesin A or higher and other thermoplastic resins are included. A method of heating and pressurizing with a press molding machine heated to the melting point or higher of the other thermoplastic resin can be used.
Two or more fabrics of the present invention may be used. Also, two or more films may be used.

Applications of the fiber-reinforced molded article of the present invention include the following.
Electric/electronic equipment (computers, displays, OA equipment, mobile phones, personal digital assistants, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (personal digital assistants such as electronic notebooks), video cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, recreational goods, toys, and other home appliances) housings, internal members (trays, chassis, etc.), internal member cases, mechanical parts, etc., industrial machine housings, building materials (Panel) etc.
Automobile, motorcycle-related parts, members and outer panels: motor parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light wheels, suspension parts, various valves (exhaust gas valves, etc.), fuel-related, exhaust systems or intake systems Pipes, air intake nozzle snorkels, intake manifolds, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors , oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, warm air flow control valve, brush holder for radiator motor, water pump impeller, Turbine vanes, wiper motor parts, distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, battery trays, AT brackets, Headlamp support, pedal housing, steering wheel, door beam, protector, chassis, frame, armrest, horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, spare tire cover, seat shell , solenoid bobbin, engine oil filter, ignition device case, under cover, scuff plate, pillar trim, propeller shaft, wheel, fender, facer, bumper, bumper beam, bonnet, aero parts, platform, cowl louver, roof, instrument panel, Spoilers, various modules, etc.
Aircraft related parts, members and skins: landing gear pods, winglets, spoilers, edges, rudders, elevators, failings, ribs, etc.
Railway-related parts, members and outer panels: bogie frames, ribs, beams, roof panels, floors, etc.
Others: Wind turbine blades, drilling jigs, drilling pipes, reinforcing tapes, fuel cell components, battery components, etc.

The fiber-reinforced molded article of the present invention is particularly preferably used for aircraft members, sporting goods, windmill blades, automobile outer panels, automobile interiors, and electronic device cases, trays, chassis, and the like.
Since the fiber-reinforced molded article of the present invention described above is obtained by molding the fabric of the present invention, the thermoplastic resin is sufficiently impregnated between the reinforcing fibers when manufacturing the fiber-reinforced molded article. Moreover, the adhesiveness between the thermoplastic resin, which is the matrix resin, and the reinforcing fibers is excellent. Therefore, it is excellent in mechanical properties such as impact resistance.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.

(Percentage of units in fluoropolymer)
The ratio of units in the fluoropolymer was determined by melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis.

(Content of adhesive functional group)
The proportion of IAH units in the fluoropolymer was determined by the following infrared absorption spectroscopy.
A 200 μm film was obtained by press-molding the fluoropolymer. The absorption peak of the IAH unit in the fluoropolymer appears at 1778 cm ⁻¹ in the infrared absorption spectrum. The absorbance of this absorption peak was measured, and the IAH unit ratio (mol%) was determined using the IAH molar extinction coefficient of 20810 mol ^-1 ·L·cm ^-1 .
Assuming that the ratio of IAH units is a (mol%), the number of adhesive functional groups (acid anhydride groups) per main chain carbon number of 1×10 ⁶ is calculated as [a×10 ⁶ /100]. .

(melting point)
Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC-7020), the melting peak was recorded when the fluoropolymer or polyamide was heated at a rate of 10 ° C./min, and the temperature corresponding to the maximum value ( °C) was taken as the melting point.

(Izod impact strength)
The sheet was cut using a contour machine (manufactured by Amada, V-400) to obtain a sample with a height of 63 mm and a width of 13 mm. A notch was made on the sample at a height of 32 mm to obtain a test piece.
For the test piece, using an Izod test device (manufactured by Toyo Seiki Seisakusho), hammer capacity: 2.75 J, hammer mass x gravity acceleration: 13.97 N, distance from the axis to the center of gravity: 10.54 cm, hitting from the axis The Izod impact strength was measured under the condition that the distance to the point was 33.5 cm.

(Melt spinnability)
A thermoplastic resin fiber was obtained by melt-spinning the fluoropolymer or resin composition by the method described in Examples. Melt spinnability was evaluated according to the following criteria.
◯: Melt spinning is possible.
Δ: Melt spinning is possible but unstable.
x: cannot be melt-spun.

(Fluororesin A)
Fluorine-containing polymer A-1:
A polymerization vessel with a stirrer having an internal volume of 430 L was degassed, and 237.2 kg of 1-hydrotridecafluorohexane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (manufactured by Asahi Glass Co., Ltd. , AK225cb, hereinafter referred to as “AK225cb”.) 49.5 kg, HFP 122 kg, and PFBE 1.31 kg were charged, the temperature in the polymerization tank was raised to 66 ° C., and a mixed gas of TFE and ethylene (TFE / ethylene = 89/11 molar ratio), the pressure was increased to 1.5 MPa [gauge]. 2.5 L of a 1-hydrotridecafluorohexane solution containing 2% by mass of tert-butyl peroxypivalate as a polymerization initiator was charged to initiate polymerization. During the polymerization, a monomer mixed gas of TFE and ethylene (TFE/ethylene=54/46 molar ratio) was continuously charged so that the pressure was kept constant. Further, PFBE in an amount corresponding to 1 mol % and IAH in an amount corresponding to 0.4 mol % were continuously charged with respect to the total number of moles of TFE and ethylene charged during polymerization. After 9.3 hours from the initiation of the polymerization, when 29 kg of the mixed monomer gas was charged, the temperature inside the polymerization tank was lowered to 25° C. and purged to normal pressure.

The obtained slurry-like fluoropolymer A-1 was charged into an 860 L granulating tank charged with 300 kg of water, and the temperature was raised to 105° C. with stirring to granulate while distilling off the solvent. . The resulting granules were dried at 150° C. for 15 hours to obtain 33.2 kg of dry granules of fluoropolymer A-1.
The ratio of each monomer unit in the fluoropolymer A-1 was TFE unit/HFP unit/PFBE unit/IAH unit/E unit=46.2/9.4/1.0/0.4/43. The content of adhesive functional groups is 3000 per 1×10 ⁶ carbon atoms in the main chain of the fluoropolymer A-1, and the melting point of the fluoropolymer A-1 is 170. °C and the melt flow rate (250°C, 21.2 N load) was 4.4 g/10 min.

Fluorine-containing polymer A-2:
A fluoropolymer A-2 was obtained in the same manner as in Example 1 of WO 2015/182702. The ratio of each unit in the fluoropolymer A-2 is TFE unit/IAH unit/PFBE unit/E unit = 58.5/0.1/2.4/39 molar ratio, and the content of the adhesive functional group The amount was 3000 for 1×10 ⁶ main chain carbon atoms of the fluoropolymer A-2, the melting point of the fluoropolymer A-2 was 245° C., and the melt flow rate (297° C., load 49N) was 22 g/10 min.

Fluorine-containing polymer A'-3: ETFE having no adhesive functional group (LM-ETFE LM-730AP, manufactured by Asahi Glass Co., melting point: 225°C, melt flow rate (297°C, load 49N): 30 g/min).

(other thermoplastic resins)
Other thermoplastic resin B-1: Polyamide 6 (UBE nylon 1022B manufactured by Ube Industries, melting point: 223°C).
Other thermoplastic resin B-2: Polyamide 66 (Leona 1500 X11 manufactured by Asahi Kasei Corporation, melting point: 265°C).
Other thermoplastic resin B-3: Polyamide 9T (manufactured by Kuraray Co., Ltd., Genestar N1000A, melting point: 300°C).

(Examples 1-3)
Fluorine-containing polymer A-1 and another thermoplastic resin B-1 were dry-blended at the ratios shown in Table 1, and charged into a twin-screw extruder (KZW15TW-45MG manufactured by Technobel Co., Ltd.). The mixture was melt-kneaded under conditions of 0 kg/hour, screw rotation speed: 200 rpm, and resin temperature setting: 240° C. to obtain a resin composition. The resulting resin composition was press-molded with a hot melt press (manufactured by Tester Sangyo Co., Ltd.) to obtain a sheet with a thickness of 2.8 mm. The press conditions were as follows: working temperature: 240° C., preheating: 6 minutes, pressure: 10 MPa, pressing time: 3 minutes. Izod impact strength was measured using the obtained sheet. Table 1 shows the results.

The obtained resin composition was supplied to a furnace body (barrel) of a melt spinning apparatus, heated and melted, extruded from a discharge die, and cooled while being pulled under tension to produce a first thermoplastic resin fiber. The spinning conditions were as follows. Melt spinnability results are shown in Table 1.
[Spinning conditions]
Furnace internal temperature: 260°C,
Shear rate (γ): 60.8 sec ^-1 ,
Stretch ratio: 1.5 to 1.6 times,
Fiber diameter: 0.65±0.01 mm.

A mixed yarn of the obtained first thermoplastic resin fiber and carbon fiber was produced, and a woven fabric was produced from the mixed yarn. Ten fabrics thus obtained were stacked to form a laminate. For the laminate, using a melt heat press (manufactured by Tester Sangyo Co., Ltd.), temperature: 260 ° C., pressure: 10 MPa, press time: 15 minutes (preheating process: 12 minutes (no pressure), compression process: 3 minutes). Press molding was performed under the conditions to obtain a laminate (fiber reinforced molded product) having a thickness of 2.3 mm (±0.05 mm). The resulting laminate had excellent adhesion between layers and good Izod impact strength.

(Comparative example 1)
A resin composition was prepared in the same manner as in Example 2 except that the fluoropolymer A'-3 was used instead of the fluoropolymer A-1 to obtain a sheet with a thickness of 2.8 mm. Izod impact strength was measured using the obtained sheet. Table 1 shows the results.
A second thermoplastic resin fiber was produced in the same manner as in Example 2, except that the resin composition of Comparative Example 1 was used instead of the resin composition of Example 2. Melt spinnability results are shown in Table 1.

(Examples 4 and 5)
Fluorine-containing polymer A-2 and another thermoplastic resin B-2 (Example 4) or another thermoplastic resin B-3 (Example 5) are dry-blended at the ratio shown in Table 1, and a twin-screw extruder is used. (manufactured by Technobell, KZW15TW-45MG), resin discharge rate: 2.0 kg / hour, screw rotation speed: 200 rpm, set resin temperature: Example 4 is 300 ° C., Example 5 is 320 ° C. The mixture was melt-kneaded to obtain a resin composition. The resulting resin composition was press-molded with a hot melt press (manufactured by Tester Sangyo Co., Ltd.) to obtain a sheet with a thickness of 2.8 mm. The pressing conditions were as follows: working temperature: 300° C. for Example 4, 320° C. for Example 5, preheating: 6 minutes, pressure: 10 MPa, pressing time: 3 minutes. Izod impact strength was measured using the obtained sheet. Table 1 shows the results.

The obtained resin composition was supplied to a furnace body (barrel) of a melt spinning apparatus, heated and melted, extruded from a discharge die, and cooled while being pulled under tension to produce a first thermoplastic resin fiber. The spinning conditions were as follows. Melt spinnability results are shown in Table 1.
[Spinning conditions]
Furnace temperature: 300°C for Example 4, 320°C for Example 5,
Shear rate (γ): 60.8 sec ^-1 ,
Stretch ratio: 1.5 to 1.6 times,
Fiber diameter: 0.65±0.01 mm.

A mixed yarn of the obtained first thermoplastic resin fiber and carbon fiber was produced, and a woven fabric was produced from the mixed yarn. Ten fabrics thus obtained were stacked to form a laminate. For the laminate, a melt heat press (manufactured by Tester Sangyo Co., Ltd.) was used, temperature: 300 ° C. for Example 4, 320 ° C. for Example 5, pressure: 10 MPa, press time: 15 minutes (preheating step: 12 minutes (heating No pressure), compression step: 3 minutes) to obtain a laminate (fiber reinforced molded article) having a thickness of 2.3 mm (±0.05 mm). The resulting laminate had excellent adhesion between layers and good Izod impact strength.

(Example 6)
Fluoropolymer A-2 was press-molded with a hot melt press (manufactured by Tester Sangyo Co., Ltd.) to obtain a sheet with a thickness of 2.8 mm. The press conditions were as follows: working temperature: 290° C., preheating: 6 minutes, pressure: 10 MPa, pressing time: 3 minutes. Izod impact strength was measured using the obtained sheet. Table 1 shows the results.

The fluoropolymer A-2 was supplied to a furnace (barrel) of a melt spinning apparatus, heated and melted, extruded from a discharge die, and cooled while being pulled under tension to produce a first thermoplastic resin fiber. . The spinning conditions were as follows. Melt spinnability results are shown in Table 1.
[Spinning conditions]
Furnace internal temperature: 270°C,
Shear rate (γ): 60.8 sec ^-1 ,
Stretch ratio: 1.5 to 1.6 times,
Fiber diameter: 0.65±0.01 mm.

A mixed yarn of the obtained first thermoplastic resin fiber and carbon fiber was produced, and a woven fabric was produced from the mixed yarn. Ten fabrics thus obtained were stacked to form a laminate. For the laminate, using a melt heat press (manufactured by Tester Sangyo Co., Ltd.), temperature: 290 ° C., pressure: 10 MPa, press time: 15 minutes (preheating process: 12 minutes (no pressure), compression process: 3 minutes). Press molding was performed under the conditions to obtain a laminate (fiber reinforced molded product) having a thickness of 2.3 mm (±0.05 mm). The resulting laminate had excellent adhesion between layers and good Izod impact strength.

The compounding ratios shown in Table 1 are in volume %, the specific gravity of the fluorine-containing polymers A-1 to A-3' is 1.75, and the specific gravity of the other thermoplastic resins B-1 to B-3 is 1.75. Calculated as 14.

The mixed yarn and fabric of the present invention are useful as raw materials and intermediates for fiber-reinforced moldings.

Claims (7)

A mixed yarn containing reinforcing fibers and first thermoplastic resin fibers,
the first thermoplastic resin fiber is a melt-moldable fluororesin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group and an isocyanate group; Including thermoplastic resins other than fluororesins,
The melt-moldable fluororesin has a melting point of 100 to 325° C.,
The thermoplastic resin other than the melt-moldable fluororesin is polyamide, polyester, polycarbonate, polybutylene terephthalate, polyarylate, polyethersulfone, polyarylsulfone, aromatic polyamide, aromatic polyetherimide, polyarylene sulfide, poly At least one selected from the group consisting of aryl ether ketone, polyamideimide, thermoplastic polyimide and liquid crystal polyester,
A mixed filament yarn, wherein the first thermoplastic resin fiber is melt-spun from the melt-moldable fluororesin and a thermoplastic resin other than the melt-moldable fluororesin. 2. The mixed fiber according to claim 1, wherein the mixed fiber yarn does not contain the melt-moldable fluororesin and further contains a second thermoplastic resin fiber containing a thermoplastic resin other than the melt-moldable fluororesin. thread. The thermoplastic resin other than the melt-moldable fluororesin is a polyamide,
The polyamides are polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 9T, polyamide 610, polyamide 612, polyamide 6/66 copolymer, polyamide 6/66/610 copolymer, polyamide 6T, polyamide 6I and polyamide MXD6. 3. The mixed filament yarn according to claim 1 or 2, which is at least one selected from the group consisting of: The mixed yarn according to any one of claims 1 to 3, wherein the reinforcing fiber is at least one selected from the group consisting of carbon fiber, glass fiber and aramid fiber. A fabric comprising the mixed yarn according to any one of claims 1 to 4. A method for producing a fiber-reinforced molded product, wherein the fabric according to claim 5 is heated to a temperature higher than the melting point of the melt-moldable fluororesin and higher than the melting point of the thermoplastic resin other than the melt-moldable fluororesin. . A laminate of the fabric according to claim 5 and a film containing either one or both of the melt-moldable fluororesin and a thermoplastic resin other than the melt-moldable fluororesin is combined with the melt-moldable fluorine resin. A method for producing a fiber-reinforced molded article, wherein the molding is performed by heating to a temperature higher than the melting point of the resin and higher than the melting point of the thermoplastic resin other than the melt-moldable fluororesin.